EP1672052B1 - Method for monitoring degradation of lubricating oils - Google Patents
Method for monitoring degradation of lubricating oils Download PDFInfo
- Publication number
- EP1672052B1 EP1672052B1 EP05257455A EP05257455A EP1672052B1 EP 1672052 B1 EP1672052 B1 EP 1672052B1 EP 05257455 A EP05257455 A EP 05257455A EP 05257455 A EP05257455 A EP 05257455A EP 1672052 B1 EP1672052 B1 EP 1672052B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- compound
- ppm
- formula
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010687 lubricating oil Substances 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 20
- 230000015556 catabolic process Effects 0.000 title claims description 16
- 238000006731 degradation reaction Methods 0.000 title claims description 16
- 238000012544 monitoring process Methods 0.000 title claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 22
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 19
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 15
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 10
- -1 nitro, hydroxy Chemical group 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 7
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 7
- 125000002015 acyclic group Chemical group 0.000 claims description 5
- 125000001589 carboacyl group Chemical group 0.000 claims description 4
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- CISNNLXXANUBPI-UHFFFAOYSA-N cyano(nitro)azanide Chemical compound [O-][N+](=O)[N-]C#N CISNNLXXANUBPI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000008033 biological extinction Effects 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003550 marker Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- VFSYQLPRXOLTOX-UHFFFAOYSA-N 1,4,5,8-tetrakis(4-butylanilino)anthracene-9,10-dione Chemical compound C1=CC(CCCC)=CC=C1NC(C=1C(=O)C2=C(NC=3C=CC(CCCC)=CC=3)C=CC(NC=3C=CC(CCCC)=CC=3)=C2C(=O)C=11)=CC=C1NC1=CC=C(CCCC)C=C1 VFSYQLPRXOLTOX-UHFFFAOYSA-N 0.000 description 3
- RYDRQRZBMBYWGG-UHFFFAOYSA-N 1,4-bis(2-ethylhexylamino)-5,8-dihydroxy-9,10-dioxoanthracene-2,3-dicarbonitrile Chemical compound O=C1C2=C(O)C=CC(O)=C2C(=O)C2=C1C(NCC(CC)CCCC)=C(C#N)C(C#N)=C2NCC(CC)CCCC RYDRQRZBMBYWGG-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- YFGXHOXJMJBGNY-UHFFFAOYSA-N 1,4,5,8-tetraanilinoanthracene-9,10-dione Chemical compound C1=CC(NC=2C=CC=CC=2)=C2C(=O)C3=C(NC=4C=CC=CC=4)C=CC(NC=4C=CC=CC=4)=C3C(=O)C2=C1NC1=CC=CC=C1 YFGXHOXJMJBGNY-UHFFFAOYSA-N 0.000 description 2
- DUJPMUKIEFLXRE-UHFFFAOYSA-N 1,4,5,8-tetrachloroanthracene-9,10-dione Chemical compound O=C1C2=C(Cl)C=CC(Cl)=C2C(=O)C2=C1C(Cl)=CC=C2Cl DUJPMUKIEFLXRE-UHFFFAOYSA-N 0.000 description 2
- SWNUSALJOQJXIX-UHFFFAOYSA-N 1,4,5,8-tetrakis(4-butylanilino)-9,10-dioxoanthracene-2,3,6,7-tetracarbonitrile Chemical compound C1=CC(CCCC)=CC=C1NC(C=1C(=O)C2=C(NC=3C=CC(CCCC)=CC=3)C(C#N)=C(C#N)C(NC=3C=CC(CCCC)=CC=3)=C2C(=O)C=11)=C(C#N)C(C#N)=C1NC1=CC=C(CCCC)C=C1 SWNUSALJOQJXIX-UHFFFAOYSA-N 0.000 description 2
- GPKSSDNORDCZPR-UHFFFAOYSA-N 1,4,5,8-tetrakis(4-butylanilino)-9,10-dioxoanthracene-2,3-dicarbonitrile Chemical compound C1=CC(CCCC)=CC=C1NC(C=1C(=O)C2=C(NC=3C=CC(CCCC)=CC=3)C(C#N)=C(C#N)C(NC=3C=CC(CCCC)=CC=3)=C2C(=O)C=11)=CC=C1NC1=CC=C(CCCC)C=C1 GPKSSDNORDCZPR-UHFFFAOYSA-N 0.000 description 2
- HJPZLFBZKDXVOA-UHFFFAOYSA-N 1,4-bis(2-ethylhexylamino)-5,8-dihydroxyanthracene-9,10-dione Chemical compound O=C1C2=C(O)C=CC(O)=C2C(=O)C2=C1C(NCC(CC)CCCC)=CC=C2NCC(CC)CCCC HJPZLFBZKDXVOA-UHFFFAOYSA-N 0.000 description 2
- MOXLRYFVOCRUEX-UHFFFAOYSA-N 1,4-bis(butylamino)-9,10-dioxoanthracene-2,3-dicarbonitrile Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=C(C#N)C(C#N)=C2NCCCC MOXLRYFVOCRUEX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- 0 *Nc(c(C(c1c2cccc1)=O)c(c(N*)c1C#N)C2=O)c1C#N Chemical compound *Nc(c(C(c1c2cccc1)=O)c(c(N*)c1C#N)C2=O)c1C#N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 description 1
- KSXHZOTTWSNEHY-UHFFFAOYSA-N 3-[3-(2-cyanoethoxy)-2,2-bis(2-cyanoethoxymethyl)propoxy]propanenitrile Chemical group N#CCCOCC(COCCC#N)(COCCC#N)COCCC#N KSXHZOTTWSNEHY-UHFFFAOYSA-N 0.000 description 1
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 description 1
- QJQPINQAQJTYMH-UHFFFAOYSA-N 5,8,9,10-tetrahydroxy-2,3-dihydroanthracene-1,4-dione Chemical compound O=C1CCC(=O)C2=C1C(O)=C1C(O)=CC=C(O)C1=C2O QJQPINQAQJTYMH-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- WONPUYDAAHCRKZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-dicarbonitrile Chemical class C1=CC(C#N)=C(C#N)C2=C1C(=O)C1=CC=CC=C1C2=O WONPUYDAAHCRKZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004476 mid-IR spectroscopy Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/007—Coloured or dyes-containing lubricant compositions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2888—Lubricating oil characteristics, e.g. deterioration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/16—Nitriles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/20—Containing nitrogen-to-oxygen bonds
- C10M2215/202—Containing nitrogen-to-oxygen bonds containing nitro groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel
- G01N33/2882—Markers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/907—Indicating means, e.g. dye, fluorescing agent
Definitions
- This invention relates generally to a method for monitoring the degradation of lubricating oils.
- Lubricating oils degrade at the high temperatures at which they often are used. A method for measuring the extent of degradation of a lubricating oil would allow timely replacement of degraded lubricants, resulting in cost savings.
- JP-A-11-281 640 discloses a method for detecting degradation of lubricating oil by using a system combining a high-speed liquid chromatograph and a spectrometer for ultraviolet and visible regions.
- the present invention relates to a method for monitoring degradation of lubricating oils.
- the method comprises steps of: (a) adding to a lubricating oil at least one compound having formula (I) wherein R 1 and R 2 independently are hydrogen, hydroxy, OR 11 , amino or NR 11 R 12 ; R 3 and R 5 independently are alkyl, aryl, aralkyl, heteroalkyl or heterocyclic; R 4 and R 6 independently are hydrogen or alkyl; R 7 , R 8 , R 9 and R 10 independently are cyano, nitro, amide, carboxyl, ester, alkyl or hydrogen; R 11 is alkyl, aryl, aralkyl, heteroalkyl, heterocyclic or alkanoyl; R 12 is hydrogen or alkyl; provided that said at least one compound of formula (I) has at least one substituent selected from among cyano, nitro, hydroxy, hydroxyalkyl, amide, carboxyl, ester and unsaturated alkyl; and (b
- lubricating oil is a natural or synthetic oil, or a mixture thereof, having suitable viscosity for use as a lubricant, e.g., as crankcase oil in an internal combustion engine, automatic transmission fluid, turbine lubricant, gear lubricant, compressor lubricant, metal-working lubricant, hydraulic fluid, etc.
- alkyl is a hydrocarbyl group having from one to twenty carbon atoms in a linear, branched or cyclic arrangement. Alkyl groups optionally have one or more double or triple bonds. Substitution on alkyl groups of one or more halo, hydroxy, alkoxy, cyano, nitro, ester, amide or carboxyl groups is permitted; these substituents may in turn be substituted by one or more halo or hydroxy substituents where possible.
- alkyl groups have no halo substituents, and in one preferred embodiment, alkyl groups are saturated, and most preferably, unsubstituted.
- a “heteroalkyl” group is an alkyl group in which at least one carbon has been replaced by O, NR, or S, wherein R is hydrogen, alkyl, aryl or aralkyl.
- An "aryl” group is a substituent derived from an aromatic hydrocarbon compound.
- An aryl group has a total of from six to twenty ring atoms, and has one or more rings which are separate or fused.
- An “aralkyl” group is an "alkyl” group substituted by an "aryl” group.
- a “heterocyclic” group is a substituent derived from a heterocyclic compound having from five to twenty ring atoms, at least one of which is nitrogen, oxygen or sulfur. Preferably, heterocyclic groups do not contain sulfur.
- aryl or heterocyclic groups of one or more of the following groups: halo, cyano, nitro, hydroxy, ester, amide, carboxyl, alkoxy, alkyl, heteroalkyl, alkanoyl, amino, or amino substituted by one or more of alkyl, aryl, aralkyl, heterocyclic, heteroalkyl or alkanoyl is permitted, with substitution by one or more halo groups permitted on substituents where possible.
- aryl and heterocyclic groups do not contain halogen atoms.
- aryl and heterocyclic groups are unsubstituted or substituted only by alkyl groups.
- An "aromatic heterocyclic" group is a heterocyclic group derived from an aromatic heterocyclic compound.
- R 4 and R 6 are hydrogen; in another embodiment, R 4 and R 6 are alkyl, preferably C 1 -C 4 saturated unsubstituted acyclic alkyl.
- R 3 , R 5 and R 11 in formula (I) are alkyl, aryl or aromatic heterocyclic. Preferably, R 3 and R 5 represent the same substituent.
- R 3 and R 5 are aryl substituted by at least one C 2 -C 20 alkyl group or aromatic heterocyclic substituted by at least one C 2 -C 20 alkyl group; alternatively, R 3 and R 5 are aryl substituted by at least one C 4 -C 20 alkyl group or aromatic heterocyclic substituted by at least one C 4 -C 20 alkyl group; preferably R 3 and R 5 are phenyl substituted by at least one C 2 -C 20 alkyl group, more preferably by at least one C 4 -C 20 alkyl group.
- R 3 and R 5 are aryl or aromatic heterocyclic groups, preferably R 4 and R 6 are hydrogen.
- R 3 and R 5 are alkyl, preferably C 2 -C 20 alkyl, more preferably C 4 -C 20 alkyl; preferably R 3 and R 5 are saturated unsubstituted alkyl.
- R 3 and R 5 are C 5 -C 8 cyclic alkyl groups; preferably R 3 and R 5 are saturated unsubstituted C 5 -C 8 cyclic alkyl groups and R 4 and R 6 are hydrogen.
- R 3 and R 5 are cyclohexyl.
- R 3 and R 5 are C 5 -C 8 cyclic alkyl groups
- R 4 and R 6 are hydrogen
- R 1 and R 2 are NR 11 R 12 , where R 12 is hydrogen and R 11 is C 5 -C 8 cyclic alkyl, preferably saturated unsubstituted alkyl; preferably R 3 and R 5 are cyclohexyl and R 1 and R 2 are cyclohexylamino.
- R 3 and R 5 are aryl substituted by at least one C 2 -C 20 alkyl group or aromatic heterocyclic substituted by at least one C 2 -C 20 alkyl group
- R 4 and R 6 are hydrogen
- R 1 and R 2 are NHR 11 , where R 11 is aryl substituted by at least one C 2 -C 20 alkyl group or aromatic heterocyclic substituted by at least one C 2 -C 20 alkyl group.
- R 7 , R 8 , R 9 and R 10 are cyano or hydrogen. In one embodiment, R 7 , R 8 , R 9 and R 10 all represent cyano. In one embodiment, R 7 and R 8 represent cyano, and R 9 and R 10 are hydrogen.
- R 1 and R 2 independently are hydrogen, hydroxy or NR 11 R 12 .
- R 11 is alkyl or aryl. In one preferred embodiment of the invention, R 11 is C 2 -C 20 alkyl.
- R 1 and R 2 represent the same substituent. Most preferably, R 1 and R 2 represent hydrogen or NR 11 R 12 .
- R 1 and R 2 are NR 11 R 12
- R 3 , R 4 , R 5 , R 6 , R 11 and R 12 are alkyl, preferably the same alkyl group; in one preferred embodiment, R 3 , R 4 , R 5 , R 6 , R 11 and R 12 are C 1 -C 4 saturated unsubstituted acyclic alkyl groups, and most preferably, methyl groups.
- a compound of formula (I) is substituted by at least one group selected from among C 2 -C 20 unsubstituted saturated acyclic alkyl groups, aryl groups substituted by at least one C 2 -C 20 alkyl group, aromatic heterocyclic groups substituted by at least one C 2 -C 20 alkyl group and C 5 -C 8 cyclic alkyl groups.
- a compound of formula (I) is substituted by at least two groups selected from among C 2 -C 20 unsubstituted saturated acyclic alkyl groups, aryl groups substituted by at least one C 2 -C 20 alkyl group, aromatic heterocyclic groups substituted by at least one C 2 -C 20 alkyl group and C 5 -C 8 cyclic alkyl groups.
- a compound of formula (I) has at least one substituent selected from among cyano, nitro, hydroxy, hydroxyalkyl, amide, carboxyl, ester and unsaturated alkyl.
- a substituent is present which is selected from among cyano, nitro, carboxyl and hydroxyalkyl, and which is present either on the anthraquinone ring, as at least one of R 7 , R 8 , R 9 and R 10 ; or it is present as a substituent on one or more of the R 3 , R 4 , R 5 , R 6 , R 11 and R 12 groups in the compound.
- Hydroxyalkyl groups are alkyl groups substituted by at least one hydroxy group, and optionally with other groups as well.
- hydroxyalkyl groups have no non-hydroxy substituents.
- Amide and ester substituents are attached at either end, e.g., both -C(O)NR 2 and -NRC(O)R are amide substituents, and both -C(O)OR and -OC(O)R are ester substituents; where "R" groups are the same or different, and represent any organic substituent groups.
- "R" groups in amide substituents are alkyl or hydrogen, and those in ester groups are alkyl.
- R 7 and R 8 are cyano
- R 4 and R 6 are hydrogen
- R 9 and R 10 are hydrogen
- a compound of formula (I) has formula (II)
- R 7 and R 8 are cyano
- R 4 and R 6 are hydrogen
- R 9 and R 10 are hydrogen
- R 1 and R 2 are hydrogen
- a compound of formula (I) has formula (III)
- R 7 and R 8 are cyano
- R 4 and R 6 are hydrogen
- R 9 and R 10 are hydrogen
- R 1 and R 2 are NHR 11
- a compound of formula (I) has formula (IV)
- R 7 , R 8 , R 9 and R 10 are cyano, R 1 and R 2 are NHR 11 , R 4 and R 6 are hydrogen, and a compound of formula (I) has formula (V).
- the amount of each compound of formula (I) added to the lubricating oil is at least 0.5 ppm, more preferably at least 1 ppm, more preferably at least 5 ppm, more preferably at least 10 ppm, and most preferably at least 100 ppm.
- the amount of each compound is less than 10,000 ppm, more preferably less than 5,000 ppm, more preferably less than 2,000 ppm and most preferably less than 1,000 ppm.
- a spectroscopic property of the lubricating oil is absorption of electromagnetic radiation in a particular frequency range, or fluorescent emission.
- amounts of compounds of formula (I) are measured by determining a spectroscopic property of the oil by exposing it to electromagnetic radiation having wavelengths in the portion of the spectrum containing the absorption maxima of the compound of formula (I), and detecting the absorption of light or fluorescent emissions. It is preferred that the detection equipment is capable of calculating concentrations and concentration ratios in a lubricating oil.
- Typical spectrophotometers known in the art are capable of detecting the compounds used in the method of this invention when they are present at a level of at least 0.5 ppm.
- the preferred cyano, nitro, hydroxy, hydroxyalkyl, amide, carboxyl, ester and unsaturated alkyl substituents degrade to other substituents having different spectroscopic characteristics, e.g., infrared (IR) and near-infrared (NIR) absorption frequencies.
- IR infrared
- NIR near-infrared
- absorption is measured in the mid-IR range, i.e., from 1500 to 2250 cm -1 , or in the NIR range from 700 to 1000 nm.
- comparison of the IR absorption intensity displayed by one of these substituents at one of its characteristic absorption frequencies with the intensity of that substituent when the compound was first introduced into the lubricating oil allows a determination of the fraction of molecules containing the substituent that have been degraded, and this in turn is correlated with the degradation of the oil.
- a cyano substituent could by hydrolyzed under operating conditions, first to an amide, and then to a carboxyl group. As the hydrolysis progresses, the characteristic IR absorption of the cyano substituent in the area of 2200 to 2250 cm -1 would gradually decrease in intensity, allowing the hydrolysis of the cyano group to be monitored.
- At least one compound of formula (I) is formulated in a solvent to facilitate its addition to the lubricating oil.
- the preferred solvents for substituted anthraquinone dyes are N-methylpyrrolidinone, N,N-dimethyl propylene urea, nitrobenzene, toluene, N,N-dimethylformamide and 2-sec-butylphenol.
- the dye is present in the solvent at a concentration of from 0.1% to 10%.
- Compounds of formula (I) also can act as markers for the lubricating oil to provide information about the oil, for example, the identity of its manufacturer. Detection of the compounds advantageously could be done by near-IR spectral analysis to take advantage of this relatively clear region in the absorption spectrum of a lubricating oil. For example, measurement of near-IR absorption in the 650 nm to 950 nm range could be used to detect the compounds.
- Example 1 Synthesis of 1,4-di-(n-butylamino)-2,3-dicyanoanthraquinone.
- Example 2 Synthesis of 1,4,5,8-tetra-(4'-n-butylphenylamino)-2,3-dicyanoanthraquinone and 1,4,5,8 -tetra(4'-n-butylphenylamino)-2,3,6,7-tetracyanoanthraquinone.
- a mixture of 10.87 g of 1,4,5,8-tetrachloroanthraquinone, 50 g of aniline, 13.4 g of potassium acetate, 1.24 g of copper sulfate, and 3.41 g of benzyl alcohol was heated to 130 °C under nitrogen and maintained at this temperature for 6.5 hours, followed by another holding period at 170 °C for 6 hours.
- the reaction mixture was cooled to ambient temperature and the precipitate was filtered to give black solids.
- Example 5 Degradation of lubricant oil and marker under high heat and oxidative conditions.
- a commercial motor oil (5W-30) containing 100 ppm of 1,4-di(2-ethylhexylamino)- 2,3 -dicyano- 5,8 -dihydroxyanthraquinone , 25 ppm Cu ++ , 10 ppm organic peroxide, 10 ppm toluenesulfonic acid, was heated to 165-170°C with air bubbling for 48 hours. Spectroscopic determination of the marker after heat aging was done in the NIR at 800 nm.
- This material has a maximum absorption band ( ⁇ max ) at a wavelength of 692 nm in xylene, or 688 nm in cyclohexane, with an extinction value of 0.640 AU in xylene and 0.660 AU in cyclohexane for a 10 mg/L solution.
Description
- This invention relates generally to a method for monitoring the degradation of lubricating oils.
- Lubricating oils degrade at the high temperatures at which they often are used. A method for measuring the extent of degradation of a lubricating oil would allow timely replacement of degraded lubricants, resulting in cost savings.
- Substituted dicyanoanthraquinones, including the following structure,
Japanese Patent Application JP61-246258 -
JP-A-11-281 640 - The present invention in its various aspects is as set out in the accompanying claims.
- The present invention relates to a method for monitoring degradation of lubricating oils. The method comprises steps of: (a) adding to a lubricating oil at least one compound having formula (I)
- All percentages are weight percentages, unless otherwise indicated. Concentrations in parts per million ("ppm") are calculated on a weight/volume basis. When a solvent is not specified for measurement of an absorption maximum, a hydrocarbon solvent is preferred. Extinction values are determined by measuring absorption in absorbance units ("AU") with a 1 cm path length on 10 mg/L solutions. A "lubricating oil" is a natural or synthetic oil, or a mixture thereof, having suitable viscosity for use as a lubricant, e.g., as crankcase oil in an internal combustion engine, automatic transmission fluid, turbine lubricant, gear lubricant, compressor lubricant, metal-working lubricant, hydraulic fluid, etc. An "alkyl" group is a hydrocarbyl group having from one to twenty carbon atoms in a linear, branched or cyclic arrangement. Alkyl groups optionally have one or more double or triple bonds. Substitution on alkyl groups of one or more halo, hydroxy, alkoxy, cyano, nitro, ester, amide or carboxyl groups is permitted; these substituents may in turn be substituted by one or more halo or hydroxy substituents where possible. Preferably, alkyl groups have no halo substituents, and in one preferred embodiment, alkyl groups are saturated, and most preferably, unsubstituted. A "heteroalkyl" group is an alkyl group in which at least one carbon has been replaced by O, NR, or S, wherein R is hydrogen, alkyl, aryl or aralkyl. An "aryl" group is a substituent derived from an aromatic hydrocarbon compound. An aryl group has a total of from six to twenty ring atoms, and has one or more rings which are separate or fused. An "aralkyl" group is an "alkyl" group substituted by an "aryl" group. A "heterocyclic" group is a substituent derived from a heterocyclic compound having from five to twenty ring atoms, at least one of which is nitrogen, oxygen or sulfur. Preferably, heterocyclic groups do not contain sulfur. Substitution on aryl or heterocyclic groups of one or more of the following groups: halo, cyano, nitro, hydroxy, ester, amide, carboxyl, alkoxy, alkyl, heteroalkyl, alkanoyl, amino, or amino substituted by one or more of alkyl, aryl, aralkyl, heterocyclic, heteroalkyl or alkanoyl is permitted, with substitution by one or more halo groups permitted on substituents where possible. Preferably, aryl and heterocyclic groups do not contain halogen atoms. In one preferred embodiment of the invention, aryl and heterocyclic groups are unsubstituted or substituted only by alkyl groups. An "aromatic heterocyclic" group is a heterocyclic group derived from an aromatic heterocyclic compound.
- In one embodiment of the invention, R4 and R6 are hydrogen; in another embodiment, R4 and R6 are alkyl, preferably C1-C4 saturated unsubstituted acyclic alkyl. In one embodiment of the invention, R3, R5 and R11 in formula (I) are alkyl, aryl or aromatic heterocyclic. Preferably, R3 and R5 represent the same substituent. In one embodiment of the invention, R3 and R5 are aryl substituted by at least one C2-C20 alkyl group or aromatic heterocyclic substituted by at least one C2-C20 alkyl group; alternatively, R3 and R5 are aryl substituted by at least one C4-C20 alkyl group or aromatic heterocyclic substituted by at least one C4-C20 alkyl group; preferably R3 and R5 are phenyl substituted by at least one C2-C20 alkyl group, more preferably by at least one C4-C20 alkyl group. When R3 and R5 are aryl or aromatic heterocyclic groups, preferably R4 and R6 are hydrogen.
- In one embodiment of the invention, R3 and R5 are alkyl, preferably C2-C20 alkyl, more preferably C4-C20 alkyl; preferably R3 and R5 are saturated unsubstituted alkyl. In one embodiment of the invention, R3 and R5 are C5-C8 cyclic alkyl groups; preferably R3 and R5 are saturated unsubstituted C5-C8 cyclic alkyl groups and R4 and R6 are hydrogen. In one preferred embodiment, R3 and R5 are cyclohexyl. In another preferred embodiment, R3 and R5 are C5-C8 cyclic alkyl groups, R4 and R6 are hydrogen, and R1 and R2 are NR11R12, where R12 is hydrogen and R11 is C5-C8 cyclic alkyl, preferably saturated unsubstituted alkyl; preferably R3 and R5 are cyclohexyl and R1 and R2 are cyclohexylamino.
- In another preferred embodiment, R3 and R5 are aryl substituted by at least one C2-C20 alkyl group or aromatic heterocyclic substituted by at least one C2-C20 alkyl group, R4 and R6 are hydrogen, and R1 and R2 are NHR11, where R11 is aryl substituted by at least one C2-C20 alkyl group or aromatic heterocyclic substituted by at least one C2-C20 alkyl group. In one embodiment, R7, R8, R9 and R10 are cyano or hydrogen. In one embodiment, R7, R8, R9 and R10 all represent cyano. In one embodiment, R7 and R8 represent cyano, and R9 and R10 are hydrogen. Preferably, R1 and R2 independently are hydrogen, hydroxy or NR11R12. Preferably, R11 is alkyl or aryl. In one preferred embodiment of the invention, R11 is C2-C20 alkyl. Preferably, R1 and R2 represent the same substituent. Most preferably, R1 and R2 represent hydrogen or NR11R12. In one embodiment, R1 and R2 are NR11R12, and R3, R4, R5, R6, R11 and R12 are alkyl, preferably the same alkyl group; in one preferred embodiment, R3, R4, R5, R6, R11 and R12 are C1-C4 saturated unsubstituted acyclic alkyl groups, and most preferably, methyl groups.
- In one embodiment, a compound of formula (I) is substituted by at least one group selected from among C2-C20 unsubstituted saturated acyclic alkyl groups, aryl groups substituted by at least one C2-C20 alkyl group, aromatic heterocyclic groups substituted by at least one C2-C20 alkyl group and C5-C8 cyclic alkyl groups. Alternatively, a compound of formula (I) is substituted by at least two groups selected from among C2-C20 unsubstituted saturated acyclic alkyl groups, aryl groups substituted by at least one C2-C20 alkyl group, aromatic heterocyclic groups substituted by at least one C2-C20 alkyl group and C5-C8 cyclic alkyl groups.
- A compound of formula (I) has at least one substituent selected from among cyano, nitro, hydroxy, hydroxyalkyl, amide, carboxyl, ester and unsaturated alkyl. Preferably, a substituent is present which is selected from among cyano, nitro, carboxyl and hydroxyalkyl, and which is present either on the anthraquinone ring, as at least one of R7, R8, R9 and R10; or it is present as a substituent on one or more of the R3, R4, R5, R6, R11 and R12 groups in the compound. Hydroxyalkyl groups are alkyl groups substituted by at least one hydroxy group, and optionally with other groups as well. In one embodiment, hydroxyalkyl groups have no non-hydroxy substituents. Amide and ester substituents are attached at either end, e.g., both -C(O)NR2 and -NRC(O)R are amide substituents, and both -C(O)OR and -OC(O)R are ester substituents; where "R" groups are the same or different, and represent any organic substituent groups. In one embodiment, "R" groups in amide substituents are alkyl or hydrogen, and those in ester groups are alkyl.
-
-
-
-
- Preferably the amount of each compound of formula (I) added to the lubricating oil is at least 0.5 ppm, more preferably at least 1 ppm, more preferably at least 5 ppm, more preferably at least 10 ppm, and most preferably at least 100 ppm. Preferably the amount of each compound is less than 10,000 ppm, more preferably less than 5,000 ppm, more preferably less than 2,000 ppm and most preferably less than 1,000 ppm.
- A spectroscopic property of the lubricating oil is absorption of electromagnetic radiation in a particular frequency range, or fluorescent emission. Preferably, amounts of compounds of formula (I) are measured by determining a spectroscopic property of the oil by exposing it to electromagnetic radiation having wavelengths in the portion of the spectrum containing the absorption maxima of the compound of formula (I), and detecting the absorption of light or fluorescent emissions. It is preferred that the detection equipment is capable of calculating concentrations and concentration ratios in a lubricating oil. Typical spectrophotometers known in the art are capable of detecting the compounds used in the method of this invention when they are present at a level of at least 0.5 ppm. It is believed that compounds of formula (I) degrade under conditions encountered in use of lubricating oils, and that measurement of the extent of that degradation by spectroscopic analysis provides useful information about the extent of degradation of the lubricating oil itself. In one embodiment, the preferred cyano, nitro, hydroxy, hydroxyalkyl, amide, carboxyl, ester and unsaturated alkyl substituents degrade to other substituents having different spectroscopic characteristics, e.g., infrared (IR) and near-infrared (NIR) absorption frequencies. Preferably, absorption is measured in the mid-IR range, i.e., from 1500 to 2250 cm-1, or in the NIR range from 700 to 1000 nm. In the present invention comparison of the IR absorption intensity displayed by one of these substituents at one of its characteristic absorption frequencies with the intensity of that substituent when the compound was first introduced into the lubricating oil allows a determination of the fraction of molecules containing the substituent that have been degraded, and this in turn is correlated with the degradation of the oil. For example, a cyano substituent could by hydrolyzed under operating conditions, first to an amide, and then to a carboxyl group. As the hydrolysis progresses, the characteristic IR absorption of the cyano substituent in the area of 2200 to 2250 cm-1 would gradually decrease in intensity, allowing the hydrolysis of the cyano group to be monitored.
- In one embodiment of the invention, at least one compound of formula (I) is formulated in a solvent to facilitate its addition to the lubricating oil. The preferred solvents for substituted anthraquinone dyes are N-methylpyrrolidinone, N,N-dimethyl propylene urea, nitrobenzene, toluene, N,N-dimethylformamide and 2-sec-butylphenol. Preferably, the dye is present in the solvent at a concentration of from 0.1% to 10%.
- Compounds of formula (I) also can act as markers for the lubricating oil to provide information about the oil, for example, the identity of its manufacturer. Detection of the compounds advantageously could be done by near-IR spectral analysis to take advantage of this relatively clear region in the absorption spectrum of a lubricating oil. For example, measurement of near-IR absorption in the 650 nm to 950 nm range could be used to detect the compounds.
- A mixture of 25.7 parts of Solvent Blue 35 {1,4- di-(n-butylamino)-anthraquinone}, 14.8 parts of NaCN, 10 parts of NH4HCO3, and 100 parts of dimethyl sulfoxide (DMSO) was allowed to react at 90-95°C for 6 hours to give 1,4-di-(n-butylamino)-2,3-dicyanoanthraquinone. This material has a maximum absorption band (λmax) at a wavelength of 700 nm in xylene with an extinction value of 0.23 AU for 10 mg/L.
- A mixture of 8.0 parts of 1,4,5,8 -tetra(4'-n-butylphenylamino)-anthraquinone, 2.53 parts of NaCN, 1.65 parts of NH4HCO3, and 39 parts of DMSO was allowed to react at 90-95°C for 6 hours to give 1,4,5,8-tetra-(4'-n-butylphenylamino)-2,3-dicyanoanthraquinone. The structure of the di-cyano product was confirmed by proton and carbon-13 NMR. This material has a maximum absorption band (λmax) at a wavelength of 835 nm in xylene with an extinction value of 0.342 AU for 10 mg/L. Longer reaction time also gave rise to the 1,4,5,8 -tetra(4'-n-butylphenylamino)-2,3,6,7-tetracyanoanthraquinone. The structure of the tetra-cyano product also was confirmed by proton and carbon-13 NMR. This material has a maximum absorption band (λmax) at a wavelength of 900 nm in xylene with an extinction value of 0.19 AU for 10 mg/L.
- A mixture of 10.87 g of 1,4,5,8-tetrachloroanthraquinone, 50 g of aniline, 13.4 g of potassium acetate, 1.24 g of copper sulfate, and 3.41 g of benzyl alcohol was heated to 130 °C under nitrogen and maintained at this temperature for 6.5 hours, followed by another holding period at 170 °C for 6 hours. The reaction mixture was cooled to ambient temperature and the precipitate was filtered to give black solids. Recrystallization of the crude product from toluene afforded 6.0 g of a dark green crystalline material (> 95% purity with the structure confirmed by proton NMR as the desired product: 1,4,5,8-tetra(phenylamino)anthraquinone. This material had a maximum absorption band (λmax) at a wavelength of 750 nm in toluene. The molar extinction coefficient (ε) was determined to be ~30,500.
- A mixture of 10.87 g of 1,4,5,8-tetrachloroanthraquinone and 95 g of 4-n-butylaniline was allowed to react at 190 °C for 12 hours. The reaction mixture was then cooled to 70 °C and diluted with an equal amount of ethanol. On standing and further cooling to ambient temperature, some precipitate was formed. The mixture was filtered, washed and recrystallized from xylenes/isopropanol to give 6.6 g of a dark green crystalline material (>95% purity) with the structure confirmed by proton NMR as the desired product of 1,4,5,8-tetra(4-n-butylphenylamino)anthraquinone. This material had a maximum absorption band (λmax) at a wavelength of 762 nm in toluene. The molar extinction coefficient (e) was determined to be ~36,900.
- A commercial motor oil (5W-30) containing 100 ppm of 1,4-di(2-ethylhexylamino)- 2,3 -dicyano- 5,8 -dihydroxyanthraquinone , 25 ppm Cu++, 10 ppm organic peroxide, 10 ppm toluenesulfonic acid, was heated to 165-170°C with air bubbling for 48 hours. Spectroscopic determination of the marker after heat aging was done in the NIR at 800 nm. The results before and after the above heat and oxidation testing are summarized as follows:
Before Heat-Aging After Heat-Aging Viscosity 12.8 cp 16.1 cp (Brookfield #2/30rpm, 20°C) TAN 0 4.9 (Total Acid #, mg KOH/g substrate) Marker Conc. 100 ppm ~ 0 ppm - These results demonstrate that the marker degrades along with the oil during heat aging, so that the marker concentration can be correlated with oil degradation.
- A mixture of 36.3 parts of 1,4-di(2-ethylhexylamino)-5,8-dihydroxyanthraquinone (derived from Example 7), 14.8 parts of NaCN, 10 parts of NH4HCO3, and 140 parts of dimethyl sulfoxide (DMSO) was allowed to react at 90-95°C for 6 hours to give 1,4-di(2-ethylhexylamino)-2,3-dicyano-5,8-dihydroxyanthraquinone. This material has a maximum absorption band (λmax) at a wavelength of 809 nm in xylene. (Ref:
JP62015260 JP61291652 - A mixture of leuco-1,4,5,8-tetrahydroxyanthraquinone (5.91 g), sodium dithionite (1.09 g) and 1-hexanol (175.2 g) was stirred while adding 2-ethylhexylamine (24.08 g). The mixture was heated to reflux (148-152°C), maintained at reflux for 6-6.5 hours, and then cooled to ambient temperature. The precipitate was collected and washed thoroughly with methanol and water, and dried. The yield of dried isolated product was 7.0 g. Approximately another 1.9 g was present in the mother liquor, for a total yield of 8.9 g (90%). The structure of the molecule was confirmed with proton NMR. This material has a maximum absorption band (λmax) at a wavelength of 692 nm in xylene, or 688 nm in cyclohexane, with an extinction value of 0.640 AU in xylene and 0.660 AU in cyclohexane for a 10 mg/L solution.
Claims (10)
- A method for monitoring degradation of lubricating oils; said method comprising steps of(a) adding to a lubricating oil at least one compound having formula (I)(b) measuring a spectroscopic property of the oil to determine degradation of said at least one compound so as to provide a comparison of the infrared absorption intensity displayed by one of the substituents at one of the substituents characteristic absorption frequencies with the infrared absorption intensity of that substituent when the compound was first introduced into the lubricating oil so as to allow a determination of the fraction of molecules containing the substituent that have been degraded, and(c) correlating the fraction of molecules containing the substituent that have been degraded with the degradation of the oil.
- The method of claim 1 in which said at least one compound of formula (I) has at least one substituent selected from among cyano, nitro, carboxyl and hydroxyalkyl.
- The method of claim 1 in which said at least one compound is present in an amount from 0.5 ppm to 5,000 ppm.
- The method of claim 3 in which the spectroscopic property is absorption of electromagnetic radiation in a 1500 to 2250 cm-1 or 700 to 1000 nm range.
- The method of claim 4 in which said at least one compound is present in an amount from 5 ppm to 2,000 ppm.
- The method of claim 1 in which said at least one compound is substituted by at least one group selected from among C2-C20 unsubstituted saturated acyclic alkyl groups, aryl groups substituted by at least one C2-C20 alkyl group, aromatic heterocyclic groups substituted by at least one C2-C20 alkyl group and C5-C8 cyclic alkyl groups.
- The method of claim 6 in which said at least one compound is present in an amount from 5 ppm to 2,000 ppm.
- The method of claim 7 in which the spectroscopic property is absorption of electromagnetic radiation in a 1500 to 2250 cm-1 or 700 to 1000 nm range.
- A method of claim 1 wherein the component of formula (I) is added to the lubricating oil in an amount of from 5 ppm to 5,000 ppm and wherein said at least one compound of formula (I) has at least one substituents selected from among cyano, nitro, carboxyl and hydroxyalkyl.
- The method of claim 9 in which said at least one compound is substituted by at least one group selected from among C2-C20 unsubstituted saturated acyclic alkyl groups, aryl groups substituted by at least one C2-C20 alkyl group, aromatic heterocyclic groups substituted by at least one C2-C20 alkyl group and C5-C8 cyclic alkyl groups.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63615304P | 2004-12-15 | 2004-12-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1672052A1 EP1672052A1 (en) | 2006-06-21 |
EP1672052B1 true EP1672052B1 (en) | 2009-02-18 |
Family
ID=36130148
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05257455A Expired - Fee Related EP1672052B1 (en) | 2004-12-15 | 2005-12-03 | Method for monitoring degradation of lubricating oils |
Country Status (3)
Country | Link |
---|---|
US (1) | US7635596B2 (en) |
EP (1) | EP1672052B1 (en) |
DE (1) | DE602005012782D1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007042254A1 (en) * | 2007-09-06 | 2009-04-02 | Carl Freudenberg Kg | Measuring device and method for analyzing the lubricant of a bearing |
RU2461812C1 (en) * | 2011-04-26 | 2012-09-20 | Государственное образовательное учреждение высшего профессионального образования "Казанский государственный энергетический университет" (КГЭУ) | Control method of technical state of high-voltage oil-filled electric power equipment |
CN102243191B (en) * | 2011-04-27 | 2013-04-17 | 洛阳轴研科技股份有限公司 | Test method for thermal ageing stability of high-temperature lubricant oil |
CN103091476B (en) * | 2011-11-04 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of quick, comprehensive oil ageing Reliable Evaluating Methods of Their Performance |
EP3237904A1 (en) * | 2014-12-24 | 2017-11-01 | Exxonmobil Research And Engineering Company | Methods for determining condition and quality of petroleum products |
DE102017219613A1 (en) * | 2017-11-06 | 2019-05-09 | Zf Friedrichshafen Ag | Control of a mixture by means of a reference spectrum |
CN110397842A (en) * | 2019-08-08 | 2019-11-01 | 广州广日电梯工业有限公司 | A kind of driving chain selfoiling system and its driving chain lubricity detection device |
CN111704557B (en) * | 2019-12-20 | 2021-02-02 | 南京晓庄学院 | Derivative |
JP2021130793A (en) * | 2020-02-21 | 2021-09-09 | 出光興産株式会社 | Deterioration measurement device, system and method, and lubricant composition |
CN111302961B (en) * | 2020-04-01 | 2022-06-14 | 中国科学院兰州化学物理研究所 | Method for synthesizing N-aryl/alkyl anthraquinone and derivatives thereof under catalysis of carbene metal ligand |
US11539317B2 (en) | 2021-04-05 | 2022-12-27 | General Electric Renovables Espana, S.L. | System and method for detecting degradation in wind turbine generator bearings |
WO2024041944A1 (en) | 2022-08-22 | 2024-02-29 | Basf Se | Novel anthraquinone-based nir absorbers |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19818176A1 (en) * | 1998-04-23 | 1999-10-28 | Basf Ag | Process for marking liquids, e.g. fuels |
US2611772A (en) * | 1950-12-30 | 1952-09-23 | Eastman Kodak Co | Preparation of 1, 4, 5, 8-tetraamino-anthraquinone compounds |
US2727045A (en) * | 1952-12-13 | 1955-12-13 | American Cyanamid Co | Preparation of alkylaminoanthraquinones |
US3164449A (en) * | 1961-03-01 | 1965-01-05 | Du Pont | Anthraquinone dyes for gasoline |
JPS54114550A (en) | 1978-02-28 | 1979-09-06 | Onoda Cement Co Ltd | Coating of inner surface of cylindrical good and its device |
IT1200452B (en) | 1985-04-12 | 1989-01-18 | Pigmenti Italia Spa | DENATURING AND MARKING COMPOSITION, PARTICULARLY SUITABLE FOR DIESEL |
JPS61246258A (en) | 1985-04-24 | 1986-11-01 | Mitsui Toatsu Chem Inc | Green dye |
JPS62903A (en) * | 1985-06-05 | 1987-01-06 | Sumitomo Chem Co Ltd | Near infrared ray absorbing filter |
JPH0662861B2 (en) | 1985-06-19 | 1994-08-17 | 三井東圧化学株式会社 | Anthraquinone-based long wavelength absorbing dye and method for producing the same |
JPS6215260A (en) | 1985-07-15 | 1987-01-23 | Mitsui Toatsu Chem Inc | Anthraquinone-type pigment absorbing long-wavelength light and production thereof |
JPH0813930B2 (en) * | 1987-12-28 | 1996-02-14 | 三井東圧化学株式会社 | High-purity anthraquinone dye for near infrared absorption filters |
US5804447A (en) * | 1992-07-23 | 1998-09-08 | Basf Aktiengesellschaft | Use of compounds which absorb and/or fluoresce in the IR region as markers for liquids |
DE4308634A1 (en) * | 1993-03-18 | 1994-09-22 | Basf Ag | Anthraquinone as a marker for mineral oils |
US5525516B1 (en) * | 1994-09-30 | 1999-11-09 | Eastman Chem Co | Method for tagging petroleum products |
JPH11281640A (en) | 1998-03-31 | 1999-10-15 | Osaka Gas Co Ltd | Method for detecting degradation of lubricating oil and controlling method |
US6274381B1 (en) * | 1998-11-09 | 2001-08-14 | Rohm And Haas Company | Method for invisibly tagging petroleum products using visible dyes |
US6811575B2 (en) * | 2001-12-20 | 2004-11-02 | Rohm And Haas Company | Method for marking hydrocarbons with anthraquinones |
US20040106526A1 (en) * | 2002-12-03 | 2004-06-03 | Baxter David Roderick | Method for marking liquid hydrocarbons |
JP3806119B2 (en) | 2003-05-23 | 2006-08-09 | ローム アンド ハース カンパニー | Method for marking hydrocarbons using substituted anthraquinones |
JP3806118B2 (en) | 2003-06-13 | 2006-08-09 | ローム アンド ハース カンパニー | Method for marking hydrocarbons with substituted anthraquinones. |
-
2005
- 2005-11-08 US US11/269,788 patent/US7635596B2/en not_active Expired - Fee Related
- 2005-12-03 EP EP05257455A patent/EP1672052B1/en not_active Expired - Fee Related
- 2005-12-03 DE DE602005012782T patent/DE602005012782D1/en active Active
Also Published As
Publication number | Publication date |
---|---|
DE602005012782D1 (en) | 2009-04-02 |
US7635596B2 (en) | 2009-12-22 |
US20060128025A1 (en) | 2006-06-15 |
EP1672052A1 (en) | 2006-06-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1672052B1 (en) | Method for monitoring degradation of lubricating oils | |
JP3806118B2 (en) | Method for marking hydrocarbons with substituted anthraquinones. | |
KR100952633B1 (en) | Method For Marking Hydrocarbons With Anthraquinones | |
EP1479749B1 (en) | Method for marking hydrocarbons with substituted anthraquinones | |
Arden-Jacob et al. | New fluorescent markers for the red region | |
KR20040007273A (en) | Pyrazinoporphyrazines As Markers For Liquid Hydrocarbons | |
JP3806114B2 (en) | Method for marking liquid hydrocarbons | |
Kanitz et al. | Preparation and characterization of bridged naphthoxazinium salts | |
US6977177B1 (en) | Method for marking hydrocarbons with substituted anthraquinones | |
Gigante et al. | Synthesis, spectroscopy, photophysics and thermal behaviour of stilbene-based triarylamines with dehydroabietic acid methyl ester moieties | |
Shao et al. | A new fluorescent triphenodioxazine dye derived from 4-aminodiphenylamine | |
CN114195797A (en) | Near-infrared fluorescent probe for mitochondrial marking | |
Jagtap | SYNTHESIS AND CHARACTERIZATION OF HIGHLY FLUORESCENT NOVEL COUMARIN CHROMOPHORES |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20051216 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK YU |
|
17Q | First examination report despatched |
Effective date: 20060912 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB IT |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602005012782 Country of ref document: DE Date of ref document: 20090402 Kind code of ref document: P |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20091119 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20181120 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20181128 Year of fee payment: 14 Ref country code: FR Payment date: 20181011 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20181220 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602005012782 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20191203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191231 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191203 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191203 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200701 |